Silver halide photographic element containing an acetylene sulfonyl compound as hardener

ABSTRACT

Acetylene sulfonyl compounds of the formula R-C*C-(CH2)n-SO2-R&#39;&#39; wherein R, R&#39;&#39; and n are defined in claims are found to be useful as hardeners for the gelatin films of light-sensitive silver halide photographic materials. Synthesis and use of these compounds also are disclosed.

Nakajima et a1.

SILVER HALIDE PHOTOGRAPI-IIC ELEMENT CONTAINING AN ACETYLENE SULFONYL COMPOUND AS HARDENER Inventors: Tomio Nakajima, Tokyo; Sadao Sugita, l-Ianno; Yukichi Kishida; Masabumi Yoshimoto; Noboru Ishida, all of Tokyo, Japan Konishiroku Photo Industry Co., Ltd.; Sankyo Company Limited, .bethqtfikxslla aa,

Filed: June 21, 1971 Appl. No.: 155,237

Assignee:

Foreign Application Priority Data June 20, 1970 Japan 45/53612 US. Cl 96/67, 96/76 R, 96/109, 96/111, 260/117, 106/125, 117/622 Int. Cl. G03c 1/76, G03c 1/48, G03c l/34, G03c 1/30 Nov. 13, 1973 [58] Field of Search 96/111, 109, 50, 96/67, 76 R; 260/117; 106/125; 117/622 [56] References Cited UNITED STATES PATENTS 3,505,071 7 4/1970 Emmi 96/111 2,816,125 12/1957 Allen et al. 96/111 X FOREIGN PATENTS OR APPLICATIONS 1,193,290 5/1970 Great Britain 96/111 Primary Examiner-J. Travis Brown Assistant Examiner-Won H. Louie, Jr. Attorney-Eric H. Waters et a1.

[57] ABSTRACT Acetylene sulfonyl compounds of the formula R--C CflCHzl PSQeiRLYXLEIQQ ELK. lld are 16- fined in claims are found to be useful as hardeners for the gelatin films of light-sensitive silver halide photographic materials. Synthesis and use of these compounds also are disclosed.

6 Claims, No Drawings SILVER HALIDE PHOTOGRAPH-NC ELEMENT CONTAlNlNG AN ACETYLENE SULFONYL COMPOUND AS HARDENER This invention relates to a hardener for the gelatin films of a light-sensitive silver halide photographic material, said hardener comprising a compound of the general formula,

R-C E C-(CH ),,SO R' wherein R is a lower alkyl group or a phenyl or alkylphenyl group; R is a hydrogen atom, a lower alkyl group or a phenyl, alkylphenyl, alkoxyphenyl or halophenyl group; and n is zero or 1.

Generally, a light-sensitive silver halide photographic material is prepared by forming various layers such as silver halide photographic emulsion layer, filter layer, inter layer, protective layer, sub layer, backing layer, etc. on a suitable support such as glass, paper or synthetic resin film. These layers are composed mainly of gelatin, so that the physical properties of said layers are dependent chiefly upon the physical properties of gelatin. However, gelatin itself is low in melting point, water-swelling and low in mechanical strength, and these properties are not desirable, or rather to say, are fatal drawbacks for the layers constituting a light-sensitive silver halide photographic material.

In view of the above, many attempts have heretofore been made to improve the physical properties of gelatin by treatment with various hardeners. These hardeners, however, have such photographic defects as being strong in desensitizing action and high in fog-forming action and, in the case of color photographic emulsions, bring about such drawbacks that they disturb the color developability of couplers or are too vigorous in hardening action to make the production of lightsensitive photographic materials difficult. Further, due particularly to the recent tendency of quick development and the adoption of automatic developing machines, the physical properties of films have come to be required more strong.

We made extensive studies on hardeners capable of giving gelatin films having such strong physical properties as to be suitable for the above-mentioned quick and automatic treatment of light-sensitive photographic materials to find that acetylene sulfones having the aforesaid general formula display excellent hardening actions without deteriorating the properties of photographic materials.

Examples of the compounds having the aforesaid general formula are as follows:

l. Eth l lentynyl sulfone HIE:

9. pTolyl p-tolylethynyl sulfone l0 rnmHg l0. p-Tolyl p-bromophenylethynyl sulfone mQ-cac-smQ-om m.p. l07-l08C l l. p-Tolyl m-methoxyphenylethynyl sulfone b.p. l65l67C/ $0113 l0 mmHg 1 2. Phenyl 3-phenyl-2-propynyl sulfone The above-mentioned compounds may be synthesized by oxidizing corresponding acetylene sulfides according to, for example, the method disclosed in Bull. Soc. Chim. Fr., 1966, 3024. Procedures for synthesis of the compounds are set forth below as reference examples.

REFERENCE EXAMPLE 1 To a solution of 7.53 g of ethyl l-pentynyl sulfide in ml. of methylene chloride is added a 0 to 5C. a solution of 48.8 g of m-chloroperbenzoic acid in 400 ml. of methylene chloride, and the resulting mixture is stirred at 0 to 5C. for 4 hours. The reaction mixture is diluted with 1.0 l. of ether, and the dilution is washed with a saturated aqueous sodium bicarbonate solution and water in this order and then dried with anhydrous sodium sulfate. Subsequently, the solvent is removed by distillation, and the residue is subjected to distillation under highly reduced pressure to obtain 5.11 g of ethyl l-pentynyl sulfone, yield 54.3%, b.p. 96-97C./- l0' mml-Ig.

REFERENCE EXAMPLE 2 To a solution of 40.2 g of l-propynyl ptolyl sulfide in 600 ml. of glacial acetic acid is added 33.8 g of 30% When applied in the above manner to a lightsensitive silver halide photographic material, the hardener of the present invention displays excellent hardening effect without adversely afiecting the fog, sensitivhydrogen peroxide, and the resulting mixture is heated 5 ity and the like photographic properties of the photoat 50 to 60C. for 2 hours. The reaction mixture is graphic emulsion. Further, even if the light-sensitive poured into 5 liters of ice water, and deposited crystals photographic material incorporated with the hardener are recovered by filtration to obtain 42.4 g of p-tolyl is stored for a long period of time, the hardener prol propynyl sulfone in the form of prisms, yield 88.2%, vides effective stability without giving any detrimental m.p. 909 1 C. effect to the photographic emulsion, and exhibits excel- The compound having the aforesaid general formula lent hardening effect even when the photographic mamay be incorporated as a gelatin film hardener into any terial is subjected to high temperature development of gelatin-containing layers constituting a lightand automatic treatment. sensitive photographic material, e.g. the sub layer, The present invention is illustrated in further detail emulsion layer, inter layer, protective layer and backbelow with reference to examples, but it is needless to lug layer, whereby the film can be hardened. Alternasay that the invention is not limited only to these, and tively, a photographic film bearing the abovevarious modifications are possible within the scope of mentioned layers may be hardened by immersing the the in ention. film in a solution of the said compound, or by dipping the film in any of the baths containing the said com- EXAMPLE 1 pound at the time of development treatment. The hardener of the Present invention y be used in combina- A silver iodobromide emulsion for photographic negtion with a known inorganic hardener such as chroative,which emulsion contains 3 mole% of silver iodide mium alum or chromium trichloride, or a known orwas charged with a gold sensitizer and then subjected ganic hardener such as formalin, glyoxal, acrolein or to second ripening. Subsequently, the emulsion was dithe like. vided into 4 portions, and one portion was coated as it In incorporating into the gelatinous layers of a lightwas on a support to prepare a control sample, while the sensitive silver halide photographic material, the hardremaining 3 portions were individually incorporated ener of the present invention is used ordinarily in the with each of methanol solutions of the previously exform of a solution in water or methanol, but may also emplified compounds (2), (7) and (10) and then be used in the form of a solution in one or more of or coated on a support to prepare samples of the present ganic solvents such as dimethylformamide and the like. invention. The amount of the hardener to be incorporated is pref- These samples were individually stored at 55C. for erably in the range of l to 20% by weight based on the 3 days, and at 50C. and RH 80% for 3 days. The thus weight of gelatin in the coating liquid. In case the hardstored samples and the fresh samples (which were imener is desired to be incorporated into a light-sensitive mediately after coating on supports) were individually silver halide emulsion layer, it is preferable to incorpoimmersed in pure water, and the temperature at which rate the hardener after the second ripening of said sileach sample was dissolved on the film surface was meaver halide emulsion. in this case, the hardener of the sured. On the other hand, the stored samples were impresent invention may be used in combination with mersed in a 3% solution of sodium carbonate monohyother ordinary additives for said photographic emuldrate at 50C., and the time required for each sample sion such as, for example, stabilizers, coating aids, sento initiate the dissolution of its film surface was measitizers or sensitizing dyes. Further, the photographic sured. Further, the samples were subjected to sensitomemulsion used may have been subjected to chemical etry to measure the values of relative speed and fog of sensitization by use of gold or sulfur, and may have the photographic emulsions. The results obtained were been incorporated with an coupler. as set forth in Table 1.

TABLE 1 Hardening characteristics Temperature required for Time required for initiation of dissolution in pure water C.) dissolution in alkali (see) Sensitivity After After Amount of characteristics After storage Alter storage hardener of emulsion Immedistorage at. C. Immedistorage at 50 C. per 10 g. ately at C. and RH ate-1y at 55 C. and RH of gelatin Relative after for 3 for after for 3 80% for Sample Emg.) Fog speed coating days 3 days coating days 3 days Control sample 0. 20 31 32 3 1 g 9 Sample incorporated with exemplified compound (2) 3 U. 16 98 (B) 180 210 Sample incorporated with exemplified compound (7) 3 0. 96 U) 91. U 200 600 Sample incorporated With exemplified compound (10) 36K) 0- 7 98 6 ('1) T5. 0 168 5 Above 65.

As is clear from the above table, the samples according to the present invention had no desensitizing action, successfully inhibited the fog and displayed excellent hardening effects.

EXAMPLE 2 The same photographic emulsion as in Example 1 was subjected to second ripening and then charged with a color coupler l-(4.'-phenoxy-3-sulfophenyl)-3- heptadecyl-S-pyrazolone. Thereafter, the emulsion was divided into 4 portions, and one portion was coated as it was on a support to prepare a control sample, while the remaining 3 portions were individually incorporated with each of aqueous solutions of the previously exemplified compounds (3), (6) and (11) and then coated on supports to prepare samples of the present invention.

These samples were individually measured to determine hardening effect in the same manner as in Example 1. Further, the samples were subjected to sensitometry by developing the samples with a color developer containing diethyl-p-phenylenediamine and effecting ordinary bleaching, fixing and water-washing treatments. The results obtained were as set forth in Table 2, in which the speed is represented by a relative speed.

EXAMPLE 3 A high speed light-sensitive silver iodobromide emulsion for roentgenography, which contained 3 mol of silver iodide was subjected to ordinary chemical ripening, and then charged with 100 ml. per liter of the emulsion of 5-methyl-7-hydroxy-s-triazolo(2.5- a)pyrimidine as a stabilizer and 2 g per liter of the emulsion of saponin as a coating aid. Subsequently, the emulsion was divided into seven portions, and one portion was coated as it was on a cellulose triacetate support to prepare a control sample, while the remaining six portions were individually coated to prepare samples of the present invention.

These samples were exposed according to the method regulated in Japanese Industrial Standards, subjected to high temperature quick development at C. for 1 minute and 30 seconds, at C. for seconds, and at 40C. for 25 seconds by use of a strongly alkaline roentgen film-developing solution containing l-phenyl-3-pyrazolidone and hydroquinone, and then measured in speed and fog. Further,.the sample were measured in hardening effects according to the same procedures as in Example 1.

Separately, the films were measured in surface strength in the following manner: Each sample was dipped for 2 minutes in a 3% sodium carbonate (mono- TABLE 2 Hardening characteristics Sensitivity Pure water bath C.) Alkali bath (sec.) characteristics of emulsion After After Amount of (immediately After storage After storage hardener after preparation) Immedistorage at C Immedistorage at 50 C per 10 g. ately at (1. and RH ately at 55 C. and RH of gelatin Relative after for 3 for after for 3 80% for Sample (mg.) Fog speed coating days 3 days coating days 3 days Control sample 0. 06 32 38 42 2. 0 2. 5 3. 2 Sample incorporated with exemplified compound 250 0. 04 56 95 Sample incorporated with exemplified compound (6) 250 0.03 98 63 122 280 Sample incorporated with exemplified compound (11) 5 0- 04 96 68 92 Above 65. b Above 300.

As is clear from Table 2, the samples according to the present invention displayed excellent hardening effects without injuring the photographic properties. Moreover, not only the couplers used were not injured in color development but also no dye stains were observed.

hydrate) solution at 50C. Immediately thereafter, the film was wiped and then scratched with a pin (R: 3 mm.). The film surface strength is expressed in terms of a load (g) with which the film surface had begun to be scratched with the pin.

The results obtained were as set forth in Table 3.

As is clear from the above table, the samples incorpohydrogen atom, a lower alkyl, phenyl, al- 

2. The material according to claim 1 wherein R is methyl, R'' is phenyl and n is zero.
 3. The material according to claim 1 wherein R is methyl, R'' is p-tolyl and n is zero.
 4. The material according to claim 1 wherein R is methyl, R'' is phenyl and n is
 1. 5. The material according to claim 1 wherein R is phenyl, R'' is methyl and n is zero.
 6. The material according to claim 1 wherein R is m-methoxyphenyl, R'' is p-tolyl and n is zero. 